Metalliferous azo dyestuffs



United States Patent METALLIFEROUS AZO DYESTUFFS Application February 5, 1954, Serial No. 408,594

Claims priority, application Switzerland February 12, 1953 8 Claims. (Cl. 260-148) No Drawing.

This invention provides new metalliferous azo dyestuffs which correspond to the general formula (1) O Me-X XMe O in which Me represents nickel or copper, X represents an oxygen atom or the group -C00 or OCH COO- R O- and R -O- each represent the radical of a hydroxynaphthalene monosulfonic acid bound to the azo linkage in ortho-position relatively to the hydroxyl group,

and in which at least one of the latter radicals contains as a further substituent a YO-O SO alkylamino group,

for example, a group of the formula YO--O S--O-CH CH NH-- in which Y represents a cation.

The invention also includes a process for making the metalliferous dyestuffs of the Formula 1, wherein a disazo-dyestufi containing ester groups and corresponding to the general formula in which U represents a hydroxyl, carboxyl or carboxy methoxy group or the radical YO--O S--O, in which Y represents a cation, and the radicals R and R have the meanings given above, is treated with an agent yielding nickel or copper.

As agents yielding nickel or copper there are advantageously used salts of divalent nickel or divalent copper such as nickel sulfate or cupric sulfate, and also compounds which contain these metals in complex union. Nickelor copper-amine complexes are especially suitable for this purpose such, for example, as the complex nickel or copper compounds obtainable from ammonia, alkyl amines such as ethylamine, morpholine, ethanolamine, pyridine, picolines or piperidine.

The disazo-dyestuffs of the Formula 2 containing ester groups, which are to be treated with the agent yielding nickel or copper, can be obtained, for example, by coupling a tetrazotized diamine of the formula (3) HX XH in which XH represents a hydroxyl, carboxyl or carboxy methoxy group, on both sides with hydroxynsphthalene sulfonic acids capable of coupling in orthoposition relatively to the hydroxyl group, at least one of which hydroxynaphthalene sulfonic acids contains as a further substituent an hydroxyalkylamino group, for example, a hydroxyethylamino group, and introducing an acid sulfuric acid ester group into the aliphatically bound hydroxyl group of the resulting disazo dyestutf.

As diamines of the Formula 3 there come into con- 2,816,102 Patented Dec. 10, 1957 ice sideration 3:3 -dihydroxy-4 4-diaminodiphenyl. 4 4'-diaminodipheny1-3:3-dicarboxylic acid and 3:3'-di-(carbomethoxy) 4 4'-diaminodiphenyl.

As hydroxynaphthalene sulfonic acids containing hydroxyalkylamino groups there are advantageously used those in which the alkyl radical is of low molecular weight, for example, a butyl, propyl or ethyl group. Furthermore, two hydroxyalkyl groups may be bound to the same nitrogen atom. The introduction of the hydroxyalkyl groups is advantageously carried out by methods in themselves known, for example, by reacting the amino group of the amino-hydroxynaphthalene sulfonic acid with a hydroxy-halogen-alkylene such as epichlorhydrin, glycerine chlorhydrin or a-chloro-'y-hydroxypropane. Especially advantageous is a-chloro-fl-hydroxyethane (glycol chlorhydrin, ethylene chlorhydrin). Furthermore, certain amino-hydroxynaphthalene sulfonic acids may be condensed with amino-hydroxyalkyl compounds, such as ethanolamine, with the aid of alkali bisulfites.

Especially valuable are the hydroxynaphthalene sulfonic acids of the formula in which n represents a whole number not greater than 2, and the group NH ,,(CH CH OH),, occupies a Bposition of the 6-membered ring I.

All the following hydroxynaphthalene sulfonic acids yield valuable dyestuffs:

Z-(B-hydroxyethyl) amino 8 hydroxynaphthalene 6- sulfonic acid,

Z-(di-B-hydroxyethyl)-amino 8 hydroxynaphthaicne 6- sulfonic acid,

2-(5 hydroxyethyl) amino 5 hydroxynaphthalenel sulfonic acid,

Z-(di-B-hydroxyethyl) amino-S-hydroxynaphthalone 7- sulfonic acid,

Z-(B-hydroxypropyl) amino 5 hydroxynaphthalene-7- sulfonic acid,

2-( -hydroxypropyl) amino 5 hydroxynaphthslene-7- sulfonic acid,

Z-(B-hydroxybutyl) amino S-hydroxynaphthalene 7- sulfonic acid and 2-(5:' -dihydroxypropylamino) 5 hydroxynaphthalene- 7-sulfonic acid.

The hydroxynaphthalene sulfonic acid containing no hydroxy-ethylamino group and which may, if desired, be used as a second coupling component may be chosen as desired. It may, of course, contain further substituents, for example, a further hydroxyl group or an amino, alkylamino, arylamino or acylamino group. As examples there may be mentioned the following compounds:

lhydroxynaphthalene-4-sulfonic acid, 2-hydroxynaphthalene-4- or 6-sulfonic acid, 2-amino-, 2-phenylamino-, Z-acetylaminoor 2-benzoylamino-S-hydroxynaphthalene- 7-sulfonic acid, or 2-amino-8-hydroxynaphthalene-fi-sulfonic acid.

Conversion of the aliphatically bound hydroxyl groups in the azo dyestuffs into acid sulfuric acid ester groups is usually carried out with advantage by the action of chlorosulfonic acid in the presence of a tertiary base, for example, a pyridine base such as picoline or pyridine itself. The dyestuffs to be esterified also contain aromatically bound hydroxyl groups, and in general no disadvantage arises if these groups are also esterified. 1n the case of hydroxyl groups which take part in a subsequent metallization and yield ortho:ortho'-dihydroxy-azo-metal complexes, the sulfuric acid ester groups are easily split ofi in which Me represents the metal nickel or copper, and R O and R;() each represent the radical of a hydroxynaphthalene mono sulfonic acid bound to the azo linkage in ortho-position relatively to the --OMe group, and in which at least one of the latter radicals contains as a further substituent a YOO S--O alkylamino group, in which Y represents a cation.

The formulae of the metalliferous dyestuffs given herein undoubtedly represent the correct stoichiometric proportions of metal and the correct position of the metal atoms in the complex. However, the distribution of main and secondary valencies in the complex union of the metal has not been established with certainty.

The new metalliferous dyestulfs of the Formula 1 are suitable for dyeing and printing a very wide variety of materials, above all cellulose-containing fibers such as linen, cotton or artificial silk and staple fibers of regenerated cellulose. The dyestufiTs are distinguished by their gOOd absorption capacity and also by their good levelling properties, and yield interesting tints of good fastness to light which are in some cases very pure, the fastness to light being maintained after the usual anticreasing treatments.

The following examples illustrate the invention, the parts and percentages being by weight:

Example I 18 parts of chlorosulfonic acid are introduced dropwise, while cooling, into 70 parts of pyridine. Into the resulting mixture there are introduced at 30-40 C., while stirring well, 18 parts of the pulverized disazodyestuif obtainable by coupling 1 mol of tetrazotized 3:3-dihydroxy-4:4-diaminodiphenyl in an alkaline medium with 2 mols of Z-(di-B-hydroxyethyl)-amino-5-hydroxynaphthalene-7-sulfonic acid, and the whole is stirred for one hour at 40 C. and for a further 2 hours at 50-55 C. The thickly liquid blue solution is diluted with a small amount of water, then rendered alkaline with sodium carbonate, the pyridine is distilled off under reduced pressure, and the dyestufi is salted out and filtered off.

In order to convert the dyestufi into its complex copper compound the paste is dissolved in 300 parts of warm water and mixed at 70 C. with ammoniacal solution of copper sulfate (corresponding to 10 parts of CUSO45H2O). The mixture is maintained at 70 C. for a few minutes, then saturated with sodium chloride and allowed to cool, whereupon the dyestulf precipitates completely in the course of several hours. The dyestuff is filtered off and dried in vacuo. It dissolves very easily in water with a blue coloration and dyes cotton very pure blue tints. The dyeing has an excellent fastness to light.

By using as starting material 16 parts of the disazodyestuif obtained by coupling tetrazotized 3:3'-dihydroxy- 4:4'-diaminodiphenyl with 2-(5-hydroxyethyD-amino 8- hydroxynaphthalene-6-sulfonic acid, and otherwise proceeding as described in this example, there is obtained a dyestuti which is likewise easily soluble and dyes cotton grey-blue tints which are very fast to light.

Example 2 18 parts of the finely pulverized dyestutf from 1 mo] of tetrazotized 3z3'-dihydroxy-4:4'-diaminodiphenyl and 2 mols of 2-(di-fi-hydroxyethylamino)-5-hydroxynaphthalene-7-sulfonic acid (see Example 1) are introduced into 150 parts of concentrated sulfuric acid, the temperature being maintained at about 30 C. by external cooling. After 2 hours the mixture is poured into ice water and saturated with sodium chloride. The dyestutf is filtered off after a few hours, washed with saturated sodium chloride solution, and converted by the method described in Example 1 into its copper complex which has approximately the same properties as the dyestuff described in the second paragraph of Example 1.

Dyestuffs having similar properties are obtained by the procedure described in this example, but by using as starting materials the disazo-dyestulfs set out in the following table. These dyestulfs are obtained by coupling 1 mol of the tetrazo-compound of the diamine named in column I with 2 mols of the coupling components given in column II:

amino-8-hydroxynaphthalene-4-sulfonic acid, there is obtained a copper complex which dyes cotton green-blue tints.

By treating the esterified dyestuffs in the manner described above with nickel sulfate, instead of copper sulfate, there are obtained easily soluble nickel complexes which dye cotton reddish blue tints of very good fastness to light.

Example 3 10 parts of the finely pulverized dyestutf from 1 mol of 4:4'-diaminodiphenyl-3 :3'-dicarboxylic acid and 2 mols of Z-(fi-hydroxyethyD-amino 5 hydroxynaphthalene-7- sulfonic acid are dissolved in parts of concentrated sulfuric acid. After one hour the solution is poured into ice water. The dyestulf is precipitated with sodium chloride and then converted into its copper complex by means of an ammoniacal solution of copper sulfate. The copper complex dissolves in water with a red-blue coloration and dyes cotton blue-violet tints.

By using, instead of the dyestuff described above, the disazo-dyestuff obtained by coupling diazotized 3:3'-di- (carboxy-methoxy)-4:4'-diaminodiphenyl with 2-(di-fihydroxyethyl)-amino-5-hydroxynaphthalene 7 sulfonic acid, there is obtained a dyestutf which yields reddish blue tints on cotton.

Example 4 100 parts of cotton are entered at 40 C. into a dye- I 5 What is claimed is: 2. A metalliferous azo dyestufi which in its free acid 1. A metalliferous azo dyestufi which in its free meld state corresponds to the formula d t th f rmula in which Me represents a metal atom having an atomic state con-e590 s o e 0 number of at least 28 and at the most 29, n is a whole number of at the most 2 and the substituents in which Me represents a metal atom having an atomic --NH (CH CH -0SO;,OH), number of at least 28 and at the most 29, m represents a 25 occupy 513mm on S of the naphthalene nuclei whole numbe o 2 t0 4, Presents a whole number 3. A cupriferous azo dyestufi which in its free acid state corresponds to the formula o--cu-0 O--Ou o (H0o,s-00H,cHi).H=-..N NH:-n(CH;CH 0BO 0H)- 501B Hots of at the most 2 and the substituents wherein n is a whole number of at the most 2, and the 0 S substituents NH,, (CH CH,OSO -OH) occupy wNHz-fl CmHam ozfloH)" B-positions of the naphthalene nuclei. n py fl-P of the p l n nuclei- 40 4. The cupriferous azo dyestufi of the formula 5. The cupriferous azo dyestufi of the formula OGu 0 6. The cupriferous azo dyestuff of the formula 7. The cupriferous azo dyestuif of the formula HOISOCHCHINH SOlE HOaS H: CH

8. The cupriferous azo dyestufi of the formula References Cited in the file of this patent FOREIGN PATENTS 333,573 Great Britain Aug. 11, 1930 553,045 Germany June 21, 1932 236,934 Switzerland July 16, 1945 236,937 Switzerland July 16, 1945 276,905 Switzerland Nov. 1, 1951 OTHER REFERENCES Georgievics et 21.: A Textbook of Dye Chemistry 1920 (pp. 6 and 7). 

1. A METALLIFEROUS AZO DYESTUFF WHICH IN ITS FREE ACID STATE CORRESPONDS TO THE FORMULA 